Method for making monomers with two quarternary amino group and (co)polymers obtained from said monomers

ABSTRACT

To prepare compound (I), a quaternising agent R 3 —X {circle over (−)}  is introduced into a solution, in an organic solvent or a mixture of organic solvents, of a compound of formula (III), at a temperature of 35 to 80° C., and the reaction is then allowed to continue at said temperature until compound (III) has disappeared completely or substantially completely, after which water is added and then an aqueous solution of compound (I) is separated and the water removed as necessary.  
                 
 
     R 1 ═H or —CH 3 ; R 2 ═ one of —CH 3 , —C 2 H 5 , —C 3 H 7  and —C 4  H 9 ; the two R 3  are the same or different and each represents one of —CH 3 , —C 2 H 5 , —C 3 H 7 , —C 4 H 9  and —CH 2 C 6 H 5 ; and the two X {circle over (−)}  are the same or different and each represents Cl {circle over (−)}  or Br {circle over (−)} .

[0001] The present invention relates to a method of manufacturingmonomers with tertiary and/or quaternary amino groups.

[0002] Compounds of the type having formula:

[0003] in which;

[0004] R⁽⁰⁾ represents H or CH₃;

[0005] A represents —O— or —NH—;

[0006] D represents a C₁-C₆ linear or branched alkylene chain;

[0007] R⁽¹⁾ and R⁽²⁾, the same or different, each representindependently H or at C₁₋₅-alkyl

[0008] are well known from the background literature.

[0009] Important compounds in this family are N,N-dimethylamino ethylacrylate (ADAME) and N,N-dimethylamino ethyl methacrylate (MADAME):

[0010] where R═H or CH₃.

[0011] A very large number of publications and patents describe themanufacture of aqueous solutions of quaternary ammonium salts((M)ADAMQUAT) based on ADAME and MADAME respectively, the mostrepresentative of these salts being expressed by the formula;

[0012] where R═H or —CH₃ and R⁽³⁾═—CH₃ or benzyl ((M)ADAMQUAT MC or(M)ADAMQUAT BZ depending on whether R⁽³⁾ represents CH₃ or benzyl).

[0013] This reaction is a quaternisation, in the presence of water, ofthe initial compound with a quaternising agent R⁽³⁾—Cl.

[0014] The resultant aqueous solutions of quaternary salts are used inparticular to prepare polymers intended for use as cationic flocculantsin the treatment of water.

[0015] During research and development work on these polymers, theapplicant company has discovered that compounds of formula (I):

[0016] in which:

[0017] R¹ represents H or —CH₃;

[0018] R² represents one of —CH₃, —C₂H₅, —C₃H₇ and —C₄H₉;

[0019] the two R³ are the same or different and each represents one of—CH₃, —C₂H₅, —C₃H₇, —C₄H₉ and —CH₂C₆H₅; and

[0020] the two X^({circle over (−)}) are the same or different and eachrepresents Cl^({circle over (−)}) or Br^({circle over (−)}),

[0021] known by CZ-A-250 962, and in particular those in which R²═CH₃,R³═CH₃ or benzyl and where X^({circle over (−)})═Cl^({circle over (−)})(which are denoted here by the abbreviation (M)ADAMQUAT 2MC or 2BZdepending on whether R³ represents CH₃ or benzyl), enable aqueousdispersions to be prepared, either saline or without salt, therebyoffering a solution to technical problems facing the person skilled inthe art, these dispersions forming the subject matter of three Frenchpatent applications filed this day in the name of the applicant company.

[0022] Accordingly, the underlying objective of the present invention isto propose a method of manufacturing compounds having formula (I) asdefined above, characterised in that at least one quaternising agent offormula (II):

R³—X^({circle over (−)})  (II)

[0023] in which R³ and X^({circle over (−)}) are as defined above, isintroduced into a solution, in an organic solvent or in a mixture oforganic solvents, of a compound having formula (III):

[0024] in which R¹ and R² are as defined above, at a temperature of 35to 80° C., then the reaction is allowed to continue at said temperature,until compound (III) has disappeared completely or substantiallycompletely, after which water is added and then an aqueous solution ofcompound (I) is separated and the water removed as necessary.

[0025] An example of a compound (I) is a compound having formula (Ia):

[0026] which may be designated by the abbreviation S-ADAMQUAT 2BZ.

[0027] Advantageously, the reaction is conducted with a molar ratio ofquaternising agent (II)/compound (III) in a range of between 1.8 and 3.

[0028] The organic solvent used is chloroform, dichloromethane ordichloroethane, for example. A mixture of such solvents may also beused.

[0029] The reaction is not generally conducted under pressure unless thequaternising agent (II) is in the gaseous state.

[0030] The quaternising agent (II) is introduced into the solution ofcompound (III), generally over a period of 0.5 to 2 hours, and, once allthe quaternising agent *has been introduced, the reaction of compounds(II) and (III) is conducted, generally over a period of 10 to 40 hours.

[0031] After separating the aqueous solution of compound (I), it ispreferable to remove all traces of organic solvent from the resultantaqueous solution by stripping in air at a reduced pressure.

[0032] Said method results in an aqueous solution with a concentrationof compound (I) which is preferably between 65 and 75% by weight.

[0033] According to one specific feature of the above method, it isconducted in the presence of at least one stabiliser selected inparticular from hydroquinone, hydroquinone methyl ether and3,5-ditert.-butyl-4-hydroxytoluene and mixtures of these stabilisers,the content of stabilising agent(s) being in particular 400 to 2000 ppmrelative to the aqueous solution of the final compound (I).

[0034] Compound (III) may be prepared by causing a compound of formula(IV):

[0035] in which R is as defined above, to react with (meth)acrylicanhydride in the presence of triethylamine, with, a molar ratio of(meth)acrylic anhydride/compound (IV) of 0.5 to 2, at a temperature of20 to 100° C., in particular 30 to 60° C., for a period of 2 to 10 hoursin the presence of at least one stabiliser such as phenothiazine,hydroquinone methyl ether, 3,5-ditert.-butyl-4-hydroxytoluene andhydroquinone and mixtures of these stabilisers in a ratio of 200 to 3000ppm relative to the charge.

[0036] In the reaction with (meth)acrylic anhydride, the triethylamineacts as a catalyst for the reaction, and traps the resultant(meth)acrylic acid in the salt form. It is generally used in anequivalent molar ratio of 1 to 2 relative to the (meth,)acrylicanhydride.

[0037] Another objective of the present invention is to proposehomopolymers or copolymers containing units of at least one monomer offormula (I) obtained by the method as defined above.

[0038] The copolymers based on the monomers (I) incorporating themonomer (Ia) may be water-soluble or hydrophobic polymers in the form ofan aqueous dispersion, latex, aqueous solution, inverse emulsion orpowder. They are prepared by radical copolymerisation using varioussynthesis methods such as polymerisation in dispersion, solution, directemulsion, inverse emulsion and inverse suspension.

[0039] The examples below, given by way of illustration only, provide aclearer understanding of,,the invention. In these examples, thespecified proportions and percentages are by weight, unless stated tothe contrary.

[0040] The following abbreviations are used in these examples:

[0041] S-ADAME: compound of formula:

[0042] EMHQ:hydroquinone methyl ether.

EXAMPLE 1 Synthesis of S-ADAME

[0043] The following are introduced into a 1 litre glass reactor:

[0044] 292 g of 1,3-bis-dimethylamino-2 propanol;

[0045] 242 g of triethylamine; and

[0046] 0.373 g of phenothiazine as a stabiliser.

[0047] 226 g of acrylic anhydride are then added to this mixture over aperiod of 1 hour at ambient temperature, under agitation and bubbling inair. The temperature increases, reaching 50° C. After an additional 2hours reaction time, the mixture is cooled and 50 ml of water are added.After decanting, 450 g of a higher organic phase are obtained, which isdistilled under reduced pressure to separate 250 g of the above compound(purity GC≧99%).

EXAMPLE 2 Quaternisation of S-ADAME to produce S-ADAMQUAT 2BZ

[0048] The S-ADAME obtained at point (a), stabilized with 1500 ppm ofhydroquinone methyl ether and 150 g of CHCl₃, is introduced in aquantity of 44.2 g into a 250 ml glass reactor. Under agitation andwhilst bubbling in air, the mixture is raised to 50° C. over a period of1 hour, 55.9 g of benzyl chloride are added. After a reaction time of 25hours, the initial acrylate has disappeared and 33 g of water are added.A higher phase is decanted and any traces of CHCl₃ removed by airstripping at 45° C. under reduced pressure (P=1.33×10⁴ Pa (100 mm Hg)).115.2 g of aqueous solution are thus obtained, containing 75% ofquaternary cationic monomer of the anticipated structure, determined byRMN ¹³C. This monomer, is called S-ADAMQUAT 2BZ.

1- Method of manufacturing a compound having formula (I):

in which: R¹ represents h or —CH₃; R² represents one of —CH₃, —C₂H₅,—C₃H₇ and —C₄H₉; the two R³ are the same or different and eachrepresents one of —CH₃, —C₂H₅, —C₃H₇, —C₄H₉ and —CH₂C₆H₅; and the twoX^({circle over (−)}) are the same or different and each representsCl^({circle over (−)}) or Br^({circle over (−)}), characterised in thatat least one quaternising agent of formula (II):R³—X^({circle over (−)})  (II) in which R³ and X^({circle over (−)}) areas defined above, is introduced into a solution, in an organic solventor in a mixture of organic solvents, of a compound having formula (III):

in which R¹ and R² are as defined above, at a temperature of 35 to 80°C., then the reaction is allowed to continue at said temperature untilcompound (III) has disappeared completely or substantially completely:after which water is added and then an aqueous solution of compound (I)is separated and the water removed as necessary. 2- Method as claimed inclaim 1, characterised in that the reaction is conducted with a molarratio of quaternising agent (II)/compound (III) in a range of between1.8 and
 3. 3- Method as claimed in one of claims 1 and 2, characterisedin that the organic solvent used is at least one selected fromchloroform, dichloromethane or dichloroethane. 4- Method as claimed inone of claims 1 to 3, characterised in that it is conducted underpressure if the quaternising agent (II) is in the gaseous state. 5-Method as claimed in one of claims 1 to 4, characterised in that thequaternising agent (II) is introduced into the solution of compound(III) over a, period of 0.5-2 hours. 6- Method as claimed in one ofclaims 1 to 5, characterised in that once: all of the quaternising agenthas been introduced, the reaction between compounds (II) and (III) isconducted for a period of between 10 and 40 hours. 7- Method as claimedin one of claims 1 to 6, characterised in that all traces,of organicsolvent are removed from the resultant aqueous solution by stripping inair at a reduced pressure. 8- Method as claimed in one of claims 1 to 7,characterised in that it produces an aqueous solution with aconcentration of65 to 75% by weight of compound 9- Method as claimed inone of claims 1 to 8, characterised in that it is conducted in thepresence of at least one stabiliser chosen in particular fromhydroquinone, hydroquinone methyl ether and3,5-ditert.-butyl-4-hydroxytoluene and mixtures of these stabilisers,the content of stabilising agent(s) being in particular from 400 to 2000ppm relative to the aqueous solution of the final compound (I). 10-Method as claimed in one of claims 1 to 9, characterised in thatcompound (III) is prepared by causing a compound of formula (IV):

in which R² is as defined above, to react with (meth)acrylic anhydridein the presence of triethylamine, with a molar ratio of (meth)acrylicanhydride/compound (IV) of 0.5 to 2, at a temperature of 20 to 100° C.,in particular 30 to 60° C., for a period of 2 to 10 hours in thepresence of at least one stabiliser such as phenothiazine, hydroquinonemethyl ether, 3,5-ditert.-butyl-4-hydroxytoluene and hydroquinone andmixtures of these stabilisers in a ratio of 200 to 3000 ppm relative tothe charge. 11- Homopolymers or copolymers containing units of at leastone monomer of formula (I) obtained by the method as defined in one ofclaims 1 to 10.